Carbamyloxybenzylidenemalononitrile

ABSTRACT

The carbamyl derivatives of 4-hydroxy-3,5-di-tert.butyl benzylidenemalononitrile are compounds which possess a high order of activity as miticides, insecticides and fungicides. New compounds of this class, for example, 3,5-di-tert.butyl-4-(3bromophenylcarbamyloxy)benzylidene-malononitrile, are particularly effective against corn rootworm while possessing less toxicity to warm blooded animals than the most closely related prior art compound.

United States Patent Cahoy et al.

[54] CARBAMYLOXYBENZYLIDENEMALO NONITRILE [72] Inventors: Roger P. Cahoy; John Sanjean, both of Overland Park, Kans.

[73] Assignee: Gulf Research 8: Development Com pany, Pittsburgh, Pa.

[22] Filed: Sept. 8, 1970 [2]] Appl. No.: 70,529

[52] US. Cl ..260/46 5 D, 260/465 F, 424/300 [51] Int. Cl ..A0ln 9/20, C07c 121/70 [58] Field of Search"; ..260/465 D [56] References Cited UNITED'STATES PATENTS 9/1970 Ozaki et al ..260/465 OTHER PUBLICATIONS Ozaki et al. Chemical Abstracts, Vol. 70, pp. 257 (1969).

[451 Sept. 26, 1972 Primary Examiner-Lewis Gotts Assistant Examiner-Dolph H. Terrence AttorneyRichard L. Kelly, Carl A. Cline, Forrest D. Stine and Howard F. Van Denburgh 5 7] ABSTRACT 5 Claims, No Drawings It has been recently discovered that certain benzyb lidenemalononitrile compounds are highly toxic to many different species of living organisms. One of these compounds, 3,S-di-tert.butyl-4-hydroxybenzylidenemalononitrile has recently been found to be effective as acaricide, insecticide and fungicide. This compound and its method of synthesis are both reported in Anno. vol. 645 p. 53-65 (1961). This compound unfortunately possesses the same disadvantage as many other highlyeffective insecticides; that is, a high level of toxicity to warm blooded animals, including humans. It has now been discovered that carbamyl derivatives of this compound having considerably higher molecular weights, which would therefore appear to dilute the toxic structure on a weight basis, possess both theadvantages of high toxicity to insects and mites and greatly reduced toxicity to warm blooded animals. The, method of preparation of these compounds is illustrated in theprocedures which appear below;

Preparation of 3,5-di-tert.butyl-4-(phenylcarbamyloxy)-benzylidenemalononitrile A stirred reaction flask was charged with 7.0 g (0.025 mole) of 3,5-di-tert.butyl-4-hydroxybenzylidenemalononitrile, 100 ml acetonitrile, 3.2 g (0.027 mole) of phenyl isocyanate and a catalytic quantity of l ,4-diazobicyclo- [2.2.2] octane. The reaction solution was heated at 60-65 for 15 hours. A small quantity of insoluble material was removed from the reaction solution by gravity filtration. The solvent was removed on a rotary evaporator and the residue was stirred with hexane. The material which crystallized was collected on a vacuum filter. The compound was crystallized from benzene hexane and melted at l35-38 C.

3 ,5-Di-tert.butyl-4-( 4-chloro-3-methylphenylcarbamyloxy)benzylidenemalononitrile was, likewise, preparation as described above. This compound melted at l3 9-4 1 C.

Anal. Calcd. for c,,H,,,clN,o,= C,69.40; H,6.27;

yl isocyanate, 1.5 ml heptane and one drop of triethylamine. The reactants were mixed by hand stirring and heated on a water bath at 50--55 C. Within several minutes, an exothermic reaction took place and the reaction temperature reached 70 C. The reaction mixture was cooled, dissolved in benzene and gravity filtered. Hexane was added to the filtrate and the precipitated oil crystallized when cooled. The material which crystallized was collected on a vacuum filter. The compound was stirred in 200 ml of heptane, collected and air dried. It melted at l4648 C.

2 Anal. Calcd. forC l'l BrN fl C,62.50; H.546;

N,8.75 Found: C,6l.87; H,5.S4;

3 ,5-Di-tert.butyl-4( 3 chloro-4-methoxyphenylcaramyloxy) benzylidenemalononitrile was, likewise, prepared as described above. This compound melted at 159-65bL C.

Anal. Calcd. for C H CIN O H.606;

C,67.02; N,9.02 C,66.30; H.6.l l;

Found:

Anal. Calcd. for C,.,H,,N,o,= Q75. 15; PL? .03;

N,l0.ll Found: c7s.7s; H,7.02;

N,9.79 The illustrative procedures for testing the com pounds as miticides and insecticides are described below;

INSECTICIDE AND Ml'l'lCIDE TESTING PROCEDURES Method for Mites, Aphids, Bean Beetles and Army Worms Three 5 oz paper cups containing Henderson dwarf lima bean plants and one 5 oz paper cup containing Orange Gem Nasturtiums, all growing in vermiculite, are placed on a turntable and sprayed to thorough wetness with 25 ml of a solution of the candidate chemical at the appropriate concentration. Nasturtiums were already infested with 50-100 beam aphids (BA). A bean plant in one paper cup bean already infested with 50-100 two-spotted mites (TSM). Leaves from the two remaining bean plants are removed following spraying and placed in disposable petri dishes with 5 southern armyworm (SA) larvae in one petri dish, and 5 Mexican bean beetle (MBB) larvae in the other petri dish. The rating is done approximately 48 hours after spraying as follows:

BA TSM* E none dead E no dead adults D l-2S% dead D l-25% dead adults C 26-50% dead B 51-75% dead A 76-l00% dead C 26-50% dead adults B 51-75% dead adults A 76-l00% dead adults Data reported here for are based on 7 days after spraying.

Method for Southern Corn Rootworm (SCR) So as to obtain more meaningful results, all tests Three 5 02 paper cups planted each with one kernel were performed at the same time of da of DeKalb XL-361 corn are treated two da planting with 10 ml of 125 y, whenever ts were held perature, light and was not controlled.

ys after possible, usually in the forenoon. All tes ppm solution of the canunder controlled conditions of tern humidity. Atmospheric pressure didate compound. Promising compounds are tested at 5 lower concentrations. The experiment is a 4 X 5 factorial in a randomized complete block design with three replications.

The tests are evaluated 9 days after ots are inspected under a dissectin treatment. The ro microscope and rated as follows:

gs given plicates. The oral oratory rats is also g the toxicity test on r ml in corn oil was employed as an additive to the diet of the animals.

SCR Rating root feeding damage lethal dose for 50 percent kill of lab recorded in the table. In conductin 5 rats, 001 g of active chemical pe ABCDE RATINGS OF COMPOUNDS ON MI'IES AND INSECTS Mexican LDm Southern bean So. corn (oral),

Conen. Mites armyworm beetle rootworm mg./kg. (p.p.m.) (TSM) (SA) (MBB) (SCR) body wt.

Compound (8) Commercial standards:

Kelthane Dicofo1.

Dursban Bux (b) New insecticides:

m B .XAAA .AAAA m AAAA AAAA .AAAE s n m a m m a mEEEEE AEEEE MAEEEE ABCCEE AADDEE H W m MAAAEE AABEE MAAAEE AAAADE AABEEE m m u m m ODE "ACCDE "ABCD mBCDEE AAAACD "ABCDE mmmmmw mmmmmm m mma mmmmmm mmmwmm w. a N N u o o o E E E t 0 i i o m H m m a b. 0 N N m o w w w m m w m m m MW fl m H Trade name.

As indicated by the tabulated data, the novel compounds of this invention possess high toxicity to southern corn rootworm while having substantially lower toxicity to warm-blooded animals. This greatly reduces the hazards involved in handling these compounds and makes it feasible to use higher concentrations in corn fields without substantial hazard to.

domestic animals and wildlife. In the typical method of use, the insecticides are formulated either as dry granules or liquid spray mixtures according to conventional techniques and are applied at planting time, with a second application, if desired, at the same time as cultivation between the corn rows. 

2. 3,5-Di-tert.butyl-4-(3-chloro-4 -methoxyphenylcarbamyloxy)benzylidenemalononitrile.
 3. 3,5-Di-tert.butyl-4-(3-bromophenylcarbamyloxy)benzilidenemalononitrile.
 4. 3,5-Di-tert.butyl-4-(2-methylphenylcarbamyloxy)benzylidenemalononitrile.
 5. 3,5-Di-tert.butyl-4-(phenylcarbamyloxy)benzylidenemalononitrile. 